title: Competing C-F activation pathways in the reaction of Pt(0) with fluoropyridines: phosphine-assistance versus oxidative addition.
abstract: A survey of computed mechanisms for C-F bond activation at the 4-position of pentafluoropyridine by the model zero-valent bis-phosphine complex, [Pt(PH3)(PH2Me)], reveals three quite distinct pathways leading to square-planar Pt(II) products. Direct oxidative addition leads to cis-[Pt(F)(4-C5NF4)(PH3)(PH2Me)] via a conventional 3-center transition state. This process competes with two different phosphine-assisted mechanisms in which C-F activation involves fluorine transfer to a phosphorus center via novel 4-center transition states. The more accessible of the two phosphine-assisted processes involves concerted transfer of an alkyl group from phosphorus to the metal to give a platinum(alkyl)(fluorophosphine), trans-[Pt(Me)(4-C5NF4)(PH3)(PH2F)], analogues of which have been observed experimentally. The second phosphine-assisted pathway sees fluorine transfer to one of the phosphine ligands with formation of a metastable metallophosphorane intermediate from which either alkyl or fluorine transfer to the metal is possible. Both Pt-fluoride and Pt(alkyl)(fluorophosphine) products are therefore accessible via this route. Our calculations highlight the central role of metallophosphorane species, either as intermediates or transition states, in aromatic C-F bond activation. In addition, the similar computed barriers for all three processes suggest that Pt-fluoride species should be accessible. This is confirmed experimentally by the reaction of [Pt(PR3)2] species (R = isopropyl (iPr), cyclohexyl (Cy), and cyclopentyl (Cyp)) with 2,3,5-trifluoro-4-(trifluoromethyl)pyridine to give cis-[Pt(F){2-C5NHF2(CF3)}(PR3)2]. These species subsequently convert to the trans-isomers, either thermally or photochemically. The crystal structure of cis-[Pt(F){2-C5NHF2(CF3)}(P iPr3)2] shows planar coordination at Pt with r(F-Pt) = 2.029(3) A and P(1)-Pt-P(2) = 109.10(3) degrees. The crystal structure of trans-[Pt(F){2-C5NHF2(CF3)}(PCyp3)2] shows standard square-planar coordination at Pt with r(F-Pt) = 2.040(19) A.
authors.affiliation: Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
authors.forename: Ainara
authors.initials: A
authors.lastname: Nova
authors.forename: Stefan
authors.initials: S
authors.lastname: Erhardt
authors.forename: Naseralla A
authors.initials: NA
authors.lastname: Jasim
authors.forename: Robin N
authors.initials: RN
authors.lastname: Perutz
authors.forename: Stuart A
authors.initials: SA
authors.lastname: Macgregor
authors.forename: John E
authors.initials: JE
authors.lastname: McGrady
authors.forename: Adrian C
authors.initials: AC
authors.lastname: Whitwood